US6043380A - Ruthenium-I0D0-optically active phosphine complex - Google Patents

Ruthenium-I0D0-optically active phosphine complex Download PDF

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US6043380A
US6043380A US09/307,750 US30775099A US6043380A US 6043380 A US6043380 A US 6043380A US 30775099 A US30775099 A US 30775099A US 6043380 A US6043380 A US 6043380A
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segphos
optically active
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binap
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Yoshiki Okeda
Tsutomu Hashimoto
Yoji Hori
Toshimitsu Hagiwara
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Takasago International Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium

Definitions

  • the present invention relates to a novel ruthenium-iodo-optically active phosphine complex and a method for the production thereof and a method for the production of an optically active 4-methyl-2-oxetanone by using the ruthenium-iodo-optically active phosphine complex, and, particularly, to the above ruthenium-iodo-optically active phosphine complex used as a catalyst for a variety of organic synthetic reactions, especially, an asymmetric hydrogenation reaction, to a method for the production of the ruthenium-iodo-optically active phosphine complex and to a method for the production of an optically active 4-methyl-2-oxetanone which is useful as intermediates, such as raw materials for polymers, raw materials for synthesizing medicines and liquid crystal materials, which are used in organic synthetic chemical industries.
  • metal complexes of a ruthenium metal and tertiary phosphine are well-known as the catalyst for asymmetric hydrogenation reactions.
  • ruthenium-optically active phosphine complex having, as a ligand, an optically active tertiary phosphine such as 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (hereinafter abbreviated as "BINAP”), the following compounds are known:
  • A represents a tertiary amine; when y is 0, x denotes 2, z denotes 4 and p denotes 1; when y is 1, x denotes 1, z denotes 1 and p denotes 0 (Japanese Patent Publication (JP-B) Nos. H4-81596 and H5-12354);
  • T represents ClO 4 , BF 4 or PF 6 ; when r is 0, x denotes 1 and y denotes 2; when r is 1, x denotes 2 and y denotes 1 (JP-B Nos. H5-12353 and H5-12355);
  • X represents a halogen atom
  • Q represents a benzene which may have a substituent or an acetonitrile
  • Y represents a halogen atom, ClO 4 , PF 6 , BPh4 (where Ph represents a phenyl group, the same as follows) or BF 4 ; when Q is benzene which may have a substituent, a, b and c all represent 1; when Q is acetonitrile and a is 0, b denotes 4 and c denotes 2; when Q is acetonitrile and a is 1, b denotes 2 and c denotes 1.
  • R' and R" respectively represent a lower alkyl group, a halogenated lower alkyl group, a phenyl group which may have a lower alkyl substituent, ⁇ -aminoalkyl group or ⁇ -aminophenylalkyl group or R' and R" may be combined with each other to form an alkylene group, and w denotes 1 or 2 (JP-B Nos. H5-11119 and H5-12355);
  • J represents a chlorine atom, a bromine atom or an iodine atom (R. Noyori et al., J. Am. Chem. Soc., Vol. 109, No. 19, pp. 5856-5859 (1987)); and
  • G represents an aryl group or a methacryl group
  • JP-A No. H10-182678 a method for the production of SEGPHOS and ruthenium complexes containing this SEGPHOS as a ligand, specifically, [RuX(arene)(SEGPHOS)] (wherein X represents a halogen atom and arene represents a hydrocarbon having a benzene ring), Ru 2 X 4 (SEGPHOS) 2 NEt 3 and Ru(methylallyl)2(SEGPHOS) are shown.
  • 4-Methylene-2-oxetanone (also called “diketene”) is hydrogenated asymmetrically in an aprotic solvent such as a methylene chloride or tetrahydrofuran by using as a catalyst [RuCl[(S)-- or (R)-BINAP(benzene)]Cl or [Ru 2 Cl 4 [(S)-- or (R)-BINAP] 2 (NEt 3 ) wherein Et represents an ethyl group (T. Ohta et al.; J. Chem. Soc., Chem. Commun., 1725 (1992)).
  • the inventors of the present invention have conducted earnest studies to solve the above problems and, as a result, found that a novel ruthenium-iodo-optically active phosphine complex which can be obtained by a relatively simple method has a remarkably high catalytic activity and can be widely used as an asymmetrically synthesizing catalyst and that when it is used as a catalyst for the asymmetric hydrogenation reaction of 4-methylene-2-oxetanone, optically active 4-methyl-2-oxetanone of optically high purity can be produced in a short time in an efficient manner, to complete the present invention.
  • ruthenium-iodo-optically active bidentate phosphine complex of the formula (1):
  • T 1 represents a carboxylic acid anion
  • SOL represents a polar solvent
  • L represents an optically active bidentate phosphine ligand
  • T 2 represents an anion different from halogen atom anions and carboxylic acid anions
  • n denotes 0 or 1
  • r denotes 0, 3 or 4
  • m denotes 1 or 2
  • q denotes 0 or 1
  • m may represents 1 or 1.5
  • p denotes 0 or 1
  • s denotes 0, 1 or 2.
  • r and s each may be 0, whilst q may be 1, or where m is 2, 1 or 1.5;
  • the ruthenium-iodo-optically active bidentate phosphine complex thus having the formula (1a):
  • L may be of the formula (2): ##STR1## wherein R 1 represents an aryl group which may have a substituent selected from the group consisting of a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a lower alkylamino group having 1 to 4 carbon atoms and a halogen atom, or a cycloalkyl group having 3 to 8 carbon atoms; and R 2 and R 3 , which may be the same or different, each represent a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms; or R 2 and R 3 may be combined to form a five-membered or six-membered ring.
  • R 1 represents an aryl group which may have a substituent selected from the group consisting of a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1
  • the method comprises reacting, in a polar solvent different from nitrile-type solvents, a ruthenium-iodo-optically active phosphine complex of the formula (3):
  • arene represents a hydrocarbon having a benzene ring and L represents an optically active bidentate phosphine ligand, either with
  • Z 1 represents an alkali metal or an alkali earth metal
  • a denotes 1 when Z 1 is an alkali metal, or 2 when Z 1 is an alkali earth metal, and T 1 has the same meaning as that defined in the formula (1);
  • Z 2 represents a mono- or di-cation of an alkali metal, an alkali earth metal, an ammonium or the like
  • T 2 represents a mono- or di-anion different from halogen atom anions and carboxylic acid anions, in which when Z 2 is a mono-cation and T is a mono-anion, b and c are each 1; when Z 2 is a mono-cation and T 2 is a di-anion, b and c denote 2 and 1, respectively; when Z 2 is a di-cation and T 2 is a di-anion, b and c are each 1, and when Z 2 is a di-cation and T 2 is a mono-anion, b and c denote 1 and 2, respectively.
  • the method may also comprise reacting, in a polar solvent different from nitrile-type solvents, a compound of formula (6):
  • arene represents a hydrocarbon having a benzene ring, with an optically active bidentate phosphine ligand L and either with
  • the optically active bidentate phosphine ligand L may be a compound selected from the group consisting of
  • R 1 represents an aryl group which may have a substituent selected from the group consisting of a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a lower alkylamino group having 1 to 4 carbon atoms and a halogen atom, or a cycloalkyl group having 3 to 8 carbon atoms;
  • an optically active tertiary phosphine H 8 --R 1 -BINAP
  • R 2 and R 3 in the formula (2) are combined with each other to form a six-membered cyclohexyl ring and which is represented by the formula (8): ##STR3## wherein R 1 is defined as indicated above in the formula (7), and; an optically active tertiary phosphine (R 1 -SEGPHOS), in which R 2 and R 3 in the formula (2) are combined with each other to form a five-membered 1,3-dioxolan ring and which is represented by the formula (9): ##STR4## wherein R 1 is defined as indicated above in the formula (7).
  • L in the formula (3) may represent R 1 -BINAP as shown in the formula (10):
  • R 1 -BINAP being defined in the formula (7).
  • L in the formula (1) may represent R 1 -BINAP as defined in the formula (7).
  • R 1 -SEGPHOS being defined in the formula (9); is reacted with the salt of the formula (5).
  • L in the formula (1) may represent R 1 -SEGPHOS as defined in the formula (9), and the ruthenium complex and R 1 -SEGPHOS may reacted with the salt of the formula (5).
  • T 1 represents a carboxylic acid anion
  • SOL represents a polar solvent
  • L represents R 1 -SEGPHOS as defined in the formula (IX)
  • T 2 represents an anion different from halogen atom anions and carboxylic acid anions
  • n denotes 0
  • m denotes 1
  • p denotes 1
  • q denotes 0 or 1
  • r denotes 3 or 4
  • s denotes 0, 1 or 2.
  • the above ruthenium-iodo-optically active bidentate phosphine complex may comprise three different complexes of formulae (12), (13) and (14):
  • R 1 -SEGPHOS represents an optically active tertiary phosphine of the formula (9)
  • SOL represents a nitrile-type polar solvent
  • T 2 designated as anion represents a perfluoroalkylsulfonyl anion.
  • the ruthenium-iodo-optically active bidentate phosphine complex wherein a ruthenium-optically active tertiary phosphine complex of the formula (11):
  • arene represents an hydrocarbon having a benzene ring and R 1 -SEGPHOS has the same meaning as defined for the formula (9); may be reacted with a perfluoroalkylsulfonate of the formula (5), in a nitrile-type polar solvent.
  • ruthenium complex of the formula (6), an optically active phosphine represented by R 1 -SEGPHOS of the formula (9), and a perfluoroalkylsulfonate of the formula (5) may be reacted in a nitrile-type polar solvent.
  • ruthenium-iodo-optically active bidentate phosphine complex examples include:
  • T 1 represents a carboxylic acid anion
  • SOL represents a polar solvent
  • L represents an optically active bidentate phosphine ligand
  • T 2 represents an anion different from halogen atom anions and carboxylic acid anions
  • n denotes 0 or 1
  • r denotes 0, 3 or 4
  • m denotes 1 or 2
  • q denotes 0 or 1, or where m is 2
  • q may represent 1 or 1.5
  • p denotes 0 or 1
  • s denotes 0, 1 or 2;
  • T 1 represents a carboxylic acid anion
  • SOL represents a polar solvent
  • L represents an optically active bidentate phosphine ligand
  • T 2 represents an anion different from halogen atom anions and carboxylic acid anions
  • n denotes 0 or 1
  • r denotes
  • m denotes 1 or 2
  • q denotes 1, or where m is 2
  • q may represent 1 or 1.5
  • p denotes 0 or 1
  • s denotes 0, and wherein said optically active bidentate phosphine ligand L is a compound selected from the group consisting of
  • R 1 represents an aryl group which may have a substituent selected from the group consisting of a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a lower alkylamino group having 1 to 4 carbon atoms and a halogen atom, or a cycloalkyl group having 3 to 8 carbon atoms;
  • an optically active tertiary phosphine H 8 --R 1 -BINAP
  • R 2 and R 3 in said formula 2 are combined with each other to form a six-membered cyclohexyl ring and which is represented by the formula (8): ##STR6## wherein R 1 is defined as indicated above in said formula (7), and; an optically active tertiary phosphine (R 1 -SEGPHOS), in which R 2 and R 3 in the formula (2) are combined with each other to form a five-membered 1,3-dioxolan ring and which is represented by the formula (9): ##STR7## wherein R 1 is defined as indicated above in the formula (7); and, (iii) three different complexes of formulae (12), (13) and (14):
  • R 1 -SEGPHOS represents an optically active tertiary phosphine of the formula (9)
  • SOL represents a nitrile-type polar solvent
  • T 2 designated as an anion represents a perfluoroalkylsulfonyl anion.
  • FIG. 1 shows the structures of [Ru(R 1 -SEGPHOS)(SOL) 4 ]I 2 , [Ru(R 1 -SEGPHOS)(SOL) 4 ]I(anion) and [RuI(R 1 -SEGPHOS)(SOL) 3 ](anion) constituting a ruthenium-iodo-optically active phosphine complex mixture of the present invention;
  • FIG. 2 is a view showing a whole LC mass spectrum of a product of Example 20;
  • FIG. 3 is an enlarged view of the LC mass spectrum of FIG. 2 in a molecular weight range between 1950 and 2030;
  • FIG. 4 is a view showing the 31 P-NMR spectrum of [Ru--I 1 .5 -- ⁇ (S)-SEGPHOS ⁇ ] 2 (OTf) obtained in Example 39;
  • FIG. 5 is a view showing the 31 P NMR spectrum of a ruthenium-iodo-optically active phosphine complex mixture obtained in Example 55;
  • FIG. 6 is a view showing the 31 P NMR spectrum of a ruthenium-iodo-optically active phosphine complex mixture obtained in Example 56;
  • FIG. 7 is a view showing the 31 P NMR spectrum of a ruthenium-iodo-optically active phosphine complex mixture obtained in Example 57;
  • FIG. 8 view showing the 31 P NMR spectrum of a ruthenium-iodo-optically active phosphine complex mixture obtained in Example 58;
  • FIG. 9 is a view showing the 31 P NMR spectrum of a ruthenium-iodo-optically active phosphine complex mixture obtained in Example 59.
  • FIG. 10 is a view showing the 31 P NMR spectrum of a ruthenium-iodo-optically active phosphine complex mixture obtained in Example 60.
  • the ruthenium-iodo-optically active phosphine complex hereinafter represented by [Ru--(I) q --(T 1 ) n (L)] m (T 2 ) p
  • [Ru--(I) q --(T 1 ) n (L)] m (T 2 ) p can be produced by the following two methods.
  • a ruthenium-optically phosphine complex [RuI(arene)(L)]I of the formula (3) is reacted with carboxylates (T 1 ) a Z 1 of the formula (4) or with salts Z 2 b (T 2 ) c of the formula (5) in a polar solvent.
  • a ruthenium complex [RuI 2 (arene)] 2 of the formula (6) is reacted with an optically active bidentate phosphine ligand and carboxylates (T 1 ) a Z 1 of the formula (4) or salts Z 2 b (T 2 ) c of the formula (5) in a polar solvent.
  • the ruthenium complex [RuI(arene)(L)]I (formula (3)) and the carboxylates (T 1 ) a Z 1 (formula (4)) or the salts Z 2 b (T 2 ) c (formula (5)) are placed in a reaction container in which air is replaced by an inert gas, e.g., nitrogen and heated with stirring in a polar solvent to react, followed by removing the polar solvent.
  • the resulting product is then stirred in a two-layer solvent of methylene chloride/water at room temperature, followed by washing, to obtain the ruthenium-iodo-optically active phosphine complex.
  • the ruthenium phosphine complex [RuI(arene)(L)]I (formula (3)) is heated with stirring in a polar solvent to react, followed by removing the polar solvent, to obtain an intermediate.
  • the intermediate are added the carboxylates (T 1 ) a Z 1 (formula (4)) or the salts Z 2 b (T 2 ) c (formula (5)) and the mixture is stirred at room temperature in a two-layer solvent of methylene chloride/water to react, thereby obtaining the ruthenium-iodo-optically active phosphine complex.
  • the ruthenium complex [RuI 2 (arene)] 2 of the formula (6), the bidentate phosphine ligand (L), and the carboxylates (T 1 ) a Z 1 (formula (4)) or the salts Z 2 b (T 2 ) c (formula (5)) are heated with stirring in a polar solvent to react, followed by removing the polar solvent.
  • the resulting product is then stirred in a two-layer solvent of methylene chloride/water at room temperature to obtain the ruthenium-iodo-optically active phosphine complex.
  • the ruthenium complex [RuI 2 (arene)] 2 (6) and the bidentate phosphine ligand (L) are heated with stirring in a polar solvent to react, followed by removing the polar solvent, to obtain an intermediate.
  • the intermediate are added the carboxylates (T 1 ) a Z 1 (formula (4)) or the salts Z 2 b (T 2 ) c (formula (5)) and the mixture is stirred at room temperature in a two-layer solvent of methylene chloride/water at room temperature to react, thereby obtaining the ruthenium-iodo-optically active phosphine complex.
  • optically active bidentate phosphine ligand represented by L in the ruthenium-optically active phosphine complex [RuI(arene)(L)]I (formula (3)) which is the raw material for the production of [Ru--(I) q --(T1) n (L)] m (T 2 ) p of the present invention optically active biphenyl tertiary phosphine (hereinafter called "BIPH" as the case may be) represented by the above-mentioned formula (2) is used.
  • BIPH examples include BIPHEP ((XXIII) described later) containing a phenyl group as R 1 , a hydrogen atom as R 2 and a methyl group as R 3 ; BICHEP ((XXIV) described later) containing a cyclohexyl group as R 1 , a hydrogen atom as R 2 and a methyl group as R 3 ; MBIPHEP ((XXV) described later) containing a phenyl group as R 1 , a hydrogen atom as R 2 and a methoxy group as R 3 ; and MBICHEP ((XXVI) described later) containing a cyclohexyl group as R 1 , a hydrogen atom as R 2 and a methoxy group as R 3 .
  • optically active biphenyl tertiary phosphine examples include, other than the above BIPHEP and the like,
  • R1-BINAP optically active tertiary phosphine
  • Examples of the aryl group represented by R 1 in R 1 -BINAP include a phenyl group, 2-naphthyl group, phenyl groups having a substituent such as a p-substituted phenyl group, m-substituted phenyl group and m-diphenyl group and 2-naphthyl groups having a substituent such as 6-substituted-2-naphthyl group.
  • Examples of the substituent which can be replaced by the phenyl group and the naphthyl group include a lower alkyl group (in which "lower” means a linear or branched chain having 1-4 carbon atoms, the same as follows) such as a methyl group and a tert-butyl group, lower alkoxy group, lower alkylamine group and halogen atom such as a chlorine atom.
  • Cycloalkyl groups having 3 to 8 carbon atoms represented by R 1 are preferable and among these groups, a cyclopentyl group and cyclohexyl group are especially preferable.
  • R 1 -BINAP As specific examples of the compounds represented by R 1 -BINAP, the following compounds may be given. Incidentally, though all tertiary phosphines embrace an (R) isomer and an (S) isomer, the notation of these isomers is omitted (the same as follows).
  • BINAP 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl
  • T-BINAP 2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl
  • tertiary phosphines may be prepared by the methods described in JP-B Nos. H4-81596, H7-33392 and H7-68260 and JP-A Nos. H1-68386 or H4-74192 and H9-124669.
  • the ruthenium-optically active phosphine complex [RuI(arene)(L)]I (formula (3)) can be obtained by the method described in JP-B No. H7-57758 or JP-A No. H5-111639.
  • the following compounds may be given.
  • R 1 -SEGPHOSs can be obtained from 3,4-methylenedioxybenzene through 5 steps according to the method described in JP-A No. H8-311211 (Publication No. H10-182678): diphenyl (3,4-methylenedioxyphenyl)phosphine oxide is prepared from a Grignard reagent of 3,4-methylenedioxybromobenzene and diphenylphosphinylchloride. The product obtained is iodized and coupled in the presence of copper powder, whereby racemic R 1 -SEGPHOS oxides are obtained. The resultant product is optically resolved and reduced by trichlorosilane, so that an optically active R1-SEGPHOS is obtained.
  • tertiary phosphine As specific examples of the tertiary phosphine, the following compounds may be given. Although all tertiary phosphines embrace an (R) isomer and an (S) isomer, the notation of these isomers is omitted (the same as follows).
  • the ruthenium-phosphine complex (11) and the perfluoroalkylsulfonate (15) are placed in a reaction container in which air is replaced by an inert gas, e.g., nitrogen and heated with stirring in a nitrile type solvent to react, followed by distilling the solvent.
  • an inert gas e.g., nitrogen
  • the resulting product is then stirred in a two-layer solvent of methylene chloride/water at room temperature, followed by washing, to obtain the ruthenium-iodo-optically active phosphine complex.
  • the ruthenium complex (6), the phosphine ligand (9) and the perfluoroalkylsulfonates (15) are heated with stirring in a nitrile type solvent to react, followed by distilling the nitrile type solvent.
  • the resulting product is then stirred in a two-layer solvent of methylene chloride/water at room temperature, followed by washing, to obtain the ruthenium-iodo-optically active phosphine complex.
  • the perfluoroalkylsulfonates represented by the compound (15) used in the present invention are used to substitute part or all of iodine ions present in the precursor of catalyst represented by the compound (5) or (7) with perfluoroalkylsulfone anions.
  • a metal or ammonium cation contained in the perfluoroalkyl-sulfonates represented by the compound (15) is combined with an iodine anion to form salts thereby removing the iodine anion from the system. Therefore, no particular limitation is imposed on the metal or ammonium cation in the perfluoroalkylsulfonates insofar as it combines with the iodine anion to form salts. Incidentally, there is no large difference between the compositions of the complexes produced by the aforementioned two methods.
  • Examples of the aryl group represented by R 1 in R 1 -SEGPHOS of the formula (4) in the ruthenium-optically active phosphine complex (11) which is the raw material used in the production of RuI a (R 1 -SEGPHOS)(SOL) b ](I) c (anion) d include a phenyl group, 2-naphthyl group, phenyl groups having a substituent such as a p-substituted phenyl group, m-substituted phenyl group and m-di-substituted-phenyl group and 2-naphthyl groups having a substituent such as 6-substituted-2-naphthyl group.
  • Examples of the substituent which can be substituted with the phenyl group and the naphthyl group include a lower alkyl group (in which "lower” means a linear or branched chain having 1-4 carbon atoms, the same as follows) such as a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group and tert-butyl group and lower alkoxy group, lower alkylamine group and halogen atom such as a chlorine atom.
  • a cyclopentyl group and a cyclohexyl group are especially preferable.
  • R 1 -SEGPHOSs can be obtained from 3,4-methylenedioxybenzene through 5 steps as mentioned above (JP-A No. H10-182678).
  • the following compounds may be given as specific examples of the tertiary phosphine. Although all tertiary phosphines embrace an (R) isomer and an (S) isomer, the notation of these isomers is omitted (the same as follows).
  • T-SEGPHOS [(5,6),(5',6')-bis(methylenedioxy)biphenyl-2,2'-diyl]bis(di-p-tolylphosphine)
  • the ruthenium-optically active phosphine complex represented by either [RuI(arene)(L)]I (3) in which L is R 1 -SEGPHOS or [RuI(arene)(R 1 -SEGPHOS)]I may be produced according to the methods described in JP-A Nos. H2-191289 and H5-111639.
  • BIPHEP As examples of BIPHEP, BICHEP, MBIPHEP and MBICHEP, similar compounds to those of SEGPHOS may be given.
  • the ruthenium-optically active phosphine complex represented by [RuI(arene)(R 1 -SEGPHOS)] may be obtained by stirring, under heat, the complex of the formula (7a) and R 1 -SEGPHOS of the formula (4a) in an organic solvent at 50° C. for about 2 hour (Patent Applications JP-A Nos. H2-191289 and H5-111639, supra).
  • examples of the hydrocarbon having a benzene ring represented by arene include benzene, toluene, xylene, mesitylene, p-cymene, hexamethylbenzene, methoxybenzene and methyl benzoate.
  • the following compounds may be given: benzene and p-cymene as examples of arene; the aforementioned SEGPHOS, T-SEGPHOS, tBu-SEGPHOS, m-T-SEGPHOS, DM-SEGPHOS, DtBu-SEGPHOS, MeO-SEGPHOS, p-Cl-SEGPHOS, Naph-SEGPHOS, cpSEGPHOS and CySEGPHOS, as examples of R 1 -SEGPHOS.
  • the ruthenium-iodo complex represented by [RuI 2 (arene)] 2 can be produced according to the method of Zelonka (R. A. Zelonka et al.; Can. J. Chem., Vol 50, 3063 (1972)).
  • Specific Examples of the resulting ruthenium-optically active phosphine complex include the following compounds:
  • the ruthenium-iodo-optically active bidentate phosphine complex represented by the formula (1) is produced by reacting the ruthenium-optically active phosphine complex [RuI(arene)(L)]I of the formula (3) either with carboxylates (T 1 ) a Z 1 of the formula (4) or with salts Z 2 b (T 2 ) c of the formula (5) in a polar solvent.
  • Examples of the carboxylates represented by the formula (4) include carboxylates of alkali metals such as lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium pyruvate, lithium benzoate, lithium trifluoroacetate, sodium formate, sodium acetate, sodium propionate, sodium butyrate, sodium pyruvate, sodium benzoate, sodium trifluoroacetate, potassium formate, potassium acetate, potassium propionate, potassium butyrate, potassium pyruvate, potassium benzoate and potassium trifluoroacetate; carboxylates of alkali earth metals such as calcium formate, calcium acetate, calcium propionate, calcium butyrate, calcium pyruvate, calcium benzoate and calcium trifluoroacetate; and other carboxylates such as silver formate, silver acetate, silver propionate, silver butyrate, silver pyruvate, silver benzoate and silver trifluoroacetate.
  • alkali metals such as lithium formate
  • salts represented by the formula (5) include sodium methane sulfonate (sodium methylate)(hereinafter abbreviated as "NaOMs”), methane sulfonate (sodium tosylate)(hereinafter abbreviated as “NaOTs”), lithium trifluoromethane sulfonate (lithium triflate)(hereinafter abbreviated as “LiOTf”), potassium nonafluorobutane sulfonate (hereinafter abbreviated as "KOS(O) 2 C 4 F 9 "), NaOTf, Mg(Otf) 2 , AgOTf, NH 4 OTf, LiBF 4 , NaBF 4 , KBF 4 , AgBF 4 , Ca(BF 4 ) 2 , NH 4 BF 4 , LiPF 6 , NaPF 6 , KPF 6 , AgPF 6 , Ca(PF 6 ) 2 , NH 4 PF 6 , LiCl
  • the amount of the carboxylates (T 1 ) a Z 1 of the formula (4) or the salts Z 2 b (T 2 ) c of the formula (5) is preferably about 0.5 to 5 equivalents by mol and more preferably about 1 to 4 equivalents by mol based on one mol of the ruthenium optically active phosphine complex [RuI(arene)(L)]I of the formula (3) or of the ruthenium complex [RuI 2 (arene)] 2 of the formula (6).
  • the ruthenium-iodo-optically active bidentate phosphine complex represented by [Ru--(I) q --(T 1 ) n (L)] m (T 2 ) p of the formula (1) in the present invention is produced either at temperatures ranging from about 40 to 60° C. and preferably from 50 to 55° C.
  • the objective ruthenium-iodo-optically active bidentate phosphine complex [Ru--(I) q --(T 1 ) n (L)] m (T 2 ) p of the formula (1) of the present invention is formed by reacting the ruthenium-optically phosphine complex [RuI(arene)(L)]I of the formula (3) with either the carboxylates (T 1 ) a Z 1 of the formula (4) or the salts Z 2 b (T 2 ) c of the formula (5), so that the arene molecule is removed from the complex formed.
  • the ruthenium-iodo-optically active bidentate phosphine complex of the formula (1) may also be formed by reacting a ruthenium complex [RuI 2 (arene)] 2 of the formula (6), an optically active bidentate phosphine, and a carboxylate (T 1 ) a Z 1 of the formula (4) or a salt Z 2 b (T 2 ) c of the formula (5), so that the arene molecule is removed from the complex formed.
  • the carboxylates are used, the complex formed has a carboxyl group in place of the iodine atom.
  • the complex formed consists of a prerequisite minimum constituents of the invention, i.e., ruthenium, iodine, a carboxyl group or a T 2 group of the salts and optically active tertiary phosphine, and is represented by [Ru--(I) q --(T 1 ) n (L)] m (T 2 ) p of the general formula (1).
  • ruthenium-iodo-optically active bidentate phosphine complex (1) of the present invention the following compounds may be given.
  • Each of the absolute configurations of the complex can be obtained, depending on which of the absolute configuration of the phosphine, (R) isomer or (S) isomer, is used. However, the notation of these isomers is omitted.
  • examples of the salts Me(anion)f represented by the formula (15) which are the raw materials for producing [RuI a (R 1 -SEGPHOS)(sol) b ](I) c (anion) d from the ruthenium complexes represented by the formulae (11) and (6) may include the following compounds.
  • LiOTf Lithium trifluoromethane sulfonate
  • NaOTf sodium trifluoromethane sulfonate
  • KOTf potassium trifluoromethane sulfonate
  • Mg(OTf) 2 Al(OTf) 3
  • AgOTf AgOTf
  • NH 4 OTf NH 4 OTf
  • LiONf Lithium nonafluorobutane sulfonate
  • NaONf sodium nonafluorobutane sulfonate
  • KONf potassium nonafluorobutane sulfonate
  • LiOhepDf Lithium heptadecafluorooctane sulfonate
  • NaOhepDf sodium heptadecafluorooctane sulfonate
  • KhepDf potassium heptadecafluorooctane sulfonate
  • NaOuDCyf Sodium undecafluorocyclohexane sulfonate
  • KuDCyf potassium undecafluorocyclohexane sulfonate
  • the amount of each of these salts is preferably in a range between about 0.25 to 2 equivalents by mol and more preferably about 0.5 to 1 equivalent by mol based on one mol of the ruthenium complex (11) or (6).
  • the nitrile type solvent used in the reaction formulae 1 and 2 are acetonitrile, benzonitrile and an acetonitrile/benzonitrile mixed solvent.
  • the temperature at which [RuI a (R 1 -SEGPHOS)(sol) b ](I) c (anion) d of the present invention is produced according to the methods 1 and 2 is about 60 to 90° C. and preferably 70 to 80° C.
  • the reaction time is about 10 to 40 hours and particularly preferably about 15 to 20 hours. After the reaction is completed, the hydrophobic organic solvent layer is taken out.
  • [RuI a (R 1 -SEGPHOS)(sol) b ](I) c (anion) d obtained in this manner is a complex having a structure in which the arene molecule of the compounds (11) and (6) is removed and the nitrile-type solvent coordinates.
  • it is a mixture of complexes having a structure in which part or all of the iodine atoms are substituted with perfluoroalkylsulfonyl anions.
  • the obtained mixture of complexes can be indicated by the formula comprising ruthenium, iodine, perfluoroalkylsulfonyl anions and optically active tertiary phosphine.
  • the complex mixture include compounds having the structures corresponding to [Ru(R 1 -SEGPHOS)(SOL) 4 ]I 2 , [Ru(R 1 -SEGPHOS)(SOL) 4 ]I(anion) and [RuI(R 1 -SEGPHOS)(SOL) 3 ](anion) of the formulae (16) to (18) shown in FIG. 1, and [Ru(R 1 -SEGPHOS)(sol) 4 ](anion) 2 .
  • These complexes are obtained as either (R) isomer or (S) isomer corresponding to the absolute configuration of R 1 -SEGPHOS (9) to be used. However, the notation of these isomers is omitted.
  • R 1 -SEGPHOS in the formulae (16) and (18) is the aforementioned SEGPHOS, T-SEGPHOS, tBu-SEGPHOS, m-T-SEGPHOS, DM-SEGPHOS, DtBu-SEGPHOS, MeO-SEGPHOS, p-Cl-SEGPHOS, Naph-SEGPHOS, cpSEGPHOS or CySEGPHOS.
  • SOL is acetonitrile (CH 3 CN) or benzonitrile (PhCN).
  • Anion is the aforementioned OTf, ONf, OhepDf or OuDCyf.
  • the complex [Ru(R 1 -SEGPHOS)(SOL) 4 ](anion) 2 is not an iodo-complex, so that it has a poor activity, it is therefore preferable to decrease the production of [Ru(R 1 -SEGPHOS)(SOL) 4 ](anion) 2 .
  • the contamination of this product causes no harm. Consequently, the iodo-complex mixture of the present invention may be used as it is prepared, without further separation or purification.
  • Optically active 4-methyl-2-oxetanone may be produced by using either [Ru--(I) q --(T 1 ) n (L)] m (T 2 ) p of the formula (1) or the complex mixture [RuI a (R 1 -SEGPHOS)(SOL) b ](I) c (anion) d as follows: either [RuI(RCOO)(R 1 -BINAP)] 2 , a specific example of the formula (1), or [RuI a (R 1 -SEGPHOS)(SOL) b ](I) c (anion) d , another specific example of the formula (1), and 4-methylene-2-oxetanone (raw material compound) and a solvent are charged into a pressure container in nitrogen atmosphere, and the mixture obtained is asymmetrically hydrogenated under a hydrogen pressure of 5 to 150 kg/cm 2 , preferably at a temperature ranging from room temperature up to 100° C.
  • 4-Methylene-2-oxetanone used as the raw material compound can be easily synthesized subsequent to the heat decomposition of acetic acid or acetic anhydride according to the method reported by R. J. Clemens et al., (Chem. Rev., Vol. 86, pp. 241-318 (1986)).
  • the catalyst [RuI(RCOO)(R 1 -BINAP)] 2 or [RuI a (R 1 -SEGPHOS)(sol) b ](I) c (anion) d is prepared, such that the molar ratio of metal ruthenium to optically active phosphine ranges from 1:1.05 to 1:0.95.
  • the optically active complex represented by the formula (3) or (11) is prepared, the optically active phosphine ligand is generally used in an amount of about 1.05 to 1.2 equivalents per equivalent of ruthenium.
  • the amount of the phosphine ligand is limited to 1.05 equivalents or less, a side reaction, that is, a polymerization reaction of 4-methylene-2-oxetanone can be avoided.
  • the amount of the optically active phosphine ligand is 0.95 equivalents or less, the amount of metal ruthenium used becomes excessive, which is economically disadvantageous.
  • the amount used as a catalyst is generally in a range between about 0.0001 and 0.01 mols and particularly preferably about 0.0002 and 0.0005 mols based on one mol of 4-methylene-2-oxetanone.
  • the amount of the catalyst is less than 0.0001 mols, only insufficient catalytic effect is obtained, whereas use of an amount exceeding 0.0005 mols is not economically advantageous.
  • the amount used as a catalyst is generally in a range between about 1/30000 and 1/2000 mols, and particularly preferably about 1/20000 and 1/10000 mols based on one mol of 4-methylene-2-oxetanone.
  • the amount of the catalyst is less than 1/30000 mols, only insufficient catalytic effect is obtained, whereas use of an amount exceeding 1/2000 mols is not economically advantageous.
  • the solvent insofar as it can be used in usual asymmetric hydrogenation.
  • the solvent may include linear or cyclic ethers such as diethyl ether, tetrahydrofuran and dioxane; organic halides such as methylene chloride, methylene bromide and dichloroethane; ketones such as acetone, methyl ethyl ketone and methyl butyl ketone; carboxylic acids such as acetic acid and propionic acid; esters such as ethyl acetate, butyl acetate and methyl 3-hydroxybutyric acid; aromatic compounds such as toluene and benzene and alcohols such as methanol, ethanol, isopropanol, tert-butyl alcohol and 1,3-butane diol and mixed solvents of these solvents.
  • About 1% of water may be further added to the above solvent to raise the rate of asymmetric hydrogenation reaction
  • the reaction temperature and reaction time in the asymmetric hydrogenation reaction differ depending on the types of catalyst and other reaction condition.
  • the reaction is generally effected at temperatures ranging from room temperature to 100° C. and preferably about 30 to 60° C. for 0.5 to 40 hours.
  • the hydrogenation pressure is in a range between about 5 to 150 kg/cm 2 and preferably about 20 to 100 kg/cm 2 .
  • the reaction product is refined by removal of the solvent or distillation, whereby the objective optically active 4-methyl-2-oxetanone having a high optical purity can be obtained efficiently in a short time span.
  • the ruthenium-iodo-optically active phosphine complexes of the invention can achieve a high asymmetric activity in asymmetric reactions, and a product of high optical purity can be obtained. Therefore, the phosphine complex of the present invention can be used widely as a catalyst for asymmetric syntheses and bring in a number of economical advantages. Particularly, when it is used as a catalyst for the asymmetric hydrogenation reaction of 4-methylene-2-oxetanone, optically active 4-methyl-2-oxetanone having a high optical purity can be produced efficiently in a short time span. This optically active 4-methyl-2-oxetanone is supplied as a useful raw material for polymer production.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.9 g (yield: 96.4%) of the titled compound.
  • a 200 ml reaction container was, after the air in the container was replaced by nitrogen, charged with 2.7 g (2.31 mmol) of [RuI(p-cymene)((S)--T-BINAP)]I and 110 ml of methanol, and the mixture was stirred at 55° C. for 16 hours. The mixture was cooled to room temperature, and methanol was withdrawn. Then, under the nitrogen atmosphere, 0.199 g (2.42 mmol) of sodium acetate was introduced into the mixture, and 20 ml of methylene chloride and 20 ml of deaerated water were further added to the resulting mixture, followed by stirring for 16 hours.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.2 g (yield: 98.6%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at room temperature under reduced pressure for 4 hours, to obtain 1.9 g (yield: 96.4%) of the titled compound.
  • a 200 ml reaction container was, after the air in the container was replaced by nitrogen, charged with 2.7 g (2.31 mmol) of [RuI(p-cymene)((S)--T-BINAP)]I, 0.199 g (2.42 mmol) of sodium acetate and 110 ml of methanol, and the mixture was stirred at 55° C. for 16 hours. The mixture was cooled to room temperature, and methanol was withdrawn. Then, under the nitrogen atmosphere, 20 ml of methylene chloride and 20 ml of deaerated water were added to the resulting mixture, followed by stirring for 30 minutes.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.2 g (yield: 98.6%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.9 g (yield: 95.0%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.0 g (yield: 95.4%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.9 g (yield: 91.3%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.9 g (yield: 93.7%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.8 g (yield: 97.0%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 40° C. under reduced pressure for 4 hours, to obtain 2.2 g (yield: 95.1%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.0 g (yield: 95.9%) of the titled compound.
  • the resulting reaction solution was distilled using a Claisen tube distiller, to obtain 18.0 g (yield: 87.5%) of a fraction having a boiling point of 71-73° C./29 mmHg (3866 Pa).
  • the conversion rate of this reaction was 87.5% and the turn-over number measured to evaluate the catalytic activity was 2630.
  • a gas chromatography analysis by comparison to a standard material confirmed that the resulting product was 4-methyl-2-oxetanone.
  • the product was subjected to a gas chromatography (GC) analysis using an optically active column (Chiraldex G-TA 30 m, manufactured by ASTEC). The result of the analysis showed that the resultant product was an (R) isomer and the optical purity was 94.3% e.e.
  • Example 12 The same procedures as in Example 12 were carried out, except that 81.58 mg (0.0794 mmol) of [RuI(PhCOO)((S)--T-BINAP)] 2 and 20.69 g (246.31 mmol) of 4-methylene-2-oxetanone were used, to obtain 17.0 g (yield: 80.3%) of the titled compound.
  • the conversion rate of this reaction was 80.1% and the turn-over number measured to evaluate the catalytic activity was 2480.
  • the measurement of the absolute configuration showed that the resulting product was an (R) isomer and the optical purity was 95.3% e.e.
  • Example 12 The same procedures as in Example 12 were carried out, except that 77.76 mg (0.0794 mmol) of [RuI(CH 3 CH 2 COO)((S)--T-BINAP)] 2 and 20.37 g (242.5 mmol) of 4-methylene-2-oxetanone were used, to obtain 15.6 g (yield: 74.8%) of the titled compound.
  • the conversion rate of this reaction was 74.97% and the turn-over number measured to evaluate the catalytic activity was 2290.
  • the measurement of the absolute configuration showed that the resulting product was an (R) isomer and the optical purity was 94.9% e.e.
  • Example 12 The same procedures as in Example 12 were carried out, except that 47.32 mg (0.0476 mmol) of [RuI(CH 3 COCOO)((S)--T-BINAP)] 2 and 20.42 g (243.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 10.6 g (yield: 50.7%) of the titled compound.
  • the conversion rate of this reaction was 50.73% and the turn-over number measured to evaluate the catalytic activity was 2590.
  • the measurement of the absolute configuration showed that the resulting product was an (R) isomer and the optical purity was 94.3% e.e.
  • Example 12 The same procedures as in Example 12 were carried out, except that 68.42 mg (0.068 mmol) of [RuI(CF 3 COO)((S)--T-BINAP)] 2 and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 15.3 g (yield: 74.7%) of the titled compound.
  • the conversion rate of this reaction was 75.0% and the turn-over number measured to evaluate the catalytic activity was 2630.
  • the measurement of the absolute configuration showed that the resulting product was an (R) isomer and the optical purity was 94.0% e.e.
  • Example 12 The same procedures as in Example 12 were carried out, except that 61.81 mg (0.068 mmol) of [RuI(CH 3 COO)((S)-BINAP)] 2 and 20.27 g (241.3 mmol) of 4-methylene-2-oxetanone were used, to obtain 14.5 g (yield: 69.9%) of the titled compound.
  • the conversion rate of this reaction was 69.9% and the turn-over number measured to evaluate the catalytic activity was 2480.
  • the measurement of the absolute configuration showed that the resulting product was an (R) isomer and the optical purity was 94.0% e.e.
  • Example 12 The same procedures as in Example 12 were carried out, except that 77.12 mg (0.068 mmol) of [RuI(CH 3 COO)((S)-tBu-BINAP)] 2 and 20.5 g (244.0 mmol) of 4-methylene-2-oxetanone were used, to obtain 14.6 g (yield: 69.5%) of the titled compound.
  • the conversion rate of this reaction was 69.7% and the turn-over number measured to evaluate the catalytic activity was 2500.
  • the measurement of the absolute configuration showed that the resulting product was an (R) isomer and the optical purity was 94.1% e.e.
  • Example 12 The same procedures as in Example 12 were carried out, except that 69.5 mg (0.068 mmol) of [RuI(CH 3 COO)((S)-DM-BINAP)] 2 and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 15.2 g (yield: 74.2%) of the titled compound.
  • the conversion rate of this reaction was 74.2% and the turn-over number measured to evaluate the catalytic activity was 2600.
  • the measurement of the absolute configuration showed that the resulting product was an (R) isomer and the optical purity was 94.2% e.e.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure.
  • the resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.05 g (yield: 97.5%) of the titled compound.
  • the analysis of the resulting product is as follows:
  • FIG. 2 is a view showing the whole LC mass spectrum of the product of Example 20.
  • the molecular weight range between 1950 and 2030 is enlarged (see FIG. 3) for further analysis
  • Measurement condition of the LC mass spectrum is as follows: HPLC condition; instrument: HP1100, transfer phase: dichloromethane, sample-dilution solvent: dichloromethane; MS condition; instrument: Micromass QUATTRO LC, ionization mode; ESI+.
  • the peak at a wavelength of 1972.9 is considered to be that of a compound having the structure below, namely, structure in which methanol is added only to the cationic portion of the product.
  • a 200 ml reaction container was, after the air in the container was replaced by nitrogen, charged with 2.7 g (2.31 mmol) of [RuI(p-cymene) ⁇ (S)T-BINAP ⁇ ]I and 110 ml of methanol, and the mixture was stirred at 55° C. for 16 hours.
  • the mixture was cooled to room temperature and methanol was withdrawn.
  • 0.416 g (2.42 mmol) of NaOTf was introduced into the mixture, followed by stirring for 16 hours.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure.
  • the resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.2 g (yield: 90.2%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.9 g (yield: 88.2%) of the titled compound.
  • a 200 ml reaction container was, after the air in the container was replaced by nitrogen, charged with 2.7 g (2.31 mmol) of [RuI(p-cymene) ⁇ (S)--T-BINAP ⁇ ]I, 0.416 g (2.42 mmol) of NaOTf and 110 ml of methanol, and the mixture was stirred at 55° C. for 16 hours. The mixture was cooled to room temperature, and methanol was withdrawn. Then, under the nitrogen atmosphere, 20 ml of methylene chloride and 20 ml of deaerated water were added to the resulting mixture, followed by stirring for 30 minutes.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.2 g (yield: 90.2%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.03 g (yield: 92.3%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.03 g (yield: 99.3%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.1 g (yield: 97.8%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.95 g (yield: 95.0%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.95 g (yield: 95.7%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.4 g (yield: 96.1%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.2 g (yield: 96.99%) of the titled compound.
  • a stainless autoclave with a volume of 500 ml was charged with 45.71 g (0.0433 mmol) of [Ru--I 1 .5 - ⁇ (S)--T-BINAP ⁇ ] 2 (OTf), 20.32 g (241.905 mmol) of 4-methylene-2-oxetanone, 80 ml of tetrahydrofuran and 0.45 ml of deaerated water under nitrogen, and the mixture was stirred at a reaction temperature of 50° C. under a hydrogen pressure of 50 kg/cm 2 for 15 hours.
  • the resulting reaction solution was distilled using a Claisen tube distiller, to obtain 16.9 (yield: 81.2%) of a fraction having a boiling point of 71-73° C./29 mmHg (3866 Pa).
  • the conversion rate of this reaction was 81.42%, and the turn-over number measured to evaluate the catalytic activity was 4550.
  • a gas chromatography analysis effected by comparison to a standard material showed that the resultant product was 4-methyl-2-oxetanone.
  • the product was subjected to a gas chromatography (GC) analysis using an optically active column (Chiraldex G-TA 30 m, manufactured by ASTEC). The result of the analysis showed that the product obtained was an (R) isomer and the optical purity was 94.5% e.e.
  • Example 31 The same procedures as in Example 31 were carried out, except that 85.55 mg (0.0794 mmol) of [Ru--I 1 .5 - ⁇ (S)--T-BINAP ⁇ ] 2 (OTs) and 20.25 g (241.07 mmol) of 4-methylene-2-oxetanone were used, to obtain 20.45 g (yield: 98.64%) of the titled compound.
  • the conversion rate of this reaction was 98.64%, and the turn-over number measured to evaluate the catalytic activity was 2990.
  • the measurement of the absolute configuration showed that the resulting product was an (R) isomer and the optical purity was 95.6% e.e.
  • Example 31 The same procedures as in Example 31 were carried out, except that 47.71 mg (0.0476 mmol) of [Ru--I 1 .5 - ⁇ (S)--T-BINAP ⁇ ] 2 (OMs) and 20.42 g (243.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 11.1 g (yield: 53.1%) of the titled compound.
  • the conversion rate of this reaction was 53.1%, and the turn-over number measured to evaluate the catalytic activity was 2710.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 94.1% e.e.
  • Example 31 The same procedures as in Example 31 were carried out, except that 50.94 mg (0.0484 mmol) of [Ru--I 1 .5 - ⁇ (S)--T-BINAP ⁇ ] 2 (PF 6 ) and 20.46 g (243.57 mmol) of 4-methylene-2-oxetanone were used, to obtain 16.3 g (yield: 77.8%) of the titled compound.
  • the conversion rate of this reaction was 77.80%, and the turn-over number measured to evaluate the catalytic activity was 3910.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 94.7% e.e.
  • Example 31 The same procedures as in Example 31 were carried out, except that 47.91 mg (0.0476 mmol) of [Ru--I 1 .5 - ⁇ (S)--T-BINAP ⁇ ] 2 (ClO 4 ) and 20.29 g (241.55 mmol) of 4-methylene-2-oxetanone were used, to obtain 15.9 g (yield: 76.5%) of the titled compound.
  • the conversion rate of this reaction was 76.5%, and the turn-over number measured to evaluate the catalytic activity was 3880.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 95.8% e.e.
  • Example 31 The same procedures as in Example 31 were carried out, except that 47.91 mg (0.0479 mmol) of [Ru--I 1 .5 - ⁇ (S)-BINAP ⁇ ] 2 (OTf) and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 15.9 g (yield: 77.65%) of the titled compound.
  • the conversion rate of this reaction was 77.65%, and the turn-over number measured to evaluate the catalytic activity was 3860.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 95.0% e.e.
  • Example 31 The same procedures as in Example 31 were carried out, except that 70.73 mg (0.0476 mmol) of [Ru--I 1 .5 - ⁇ (S)-p-tBu-BINAP ⁇ ] 2 (OTf) and 20.34 g (242.14 mmol) of 4-methylene-2-oxetanone were used, to obtain 12.4 g (yield: 59.55%) of the titled compound.
  • the conversion rate of this reaction was 59.65%, and the turn-over number measured to evaluate the catalytic activity was 3030.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 95.8%e.e.
  • Example 31 The same procedures as in Example 31 were carried out, except that 69.5 mg (0.0625 mmol) of [Ru--I 1 .5 - ⁇ (S)-DM-BINAP ⁇ ] 2 (OTf) and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 19.3 g (yield: 94.2%) of the titled compound.
  • the conversion rate of this reaction was 94.2%, and the turn-over number measured to evaluate the catalytic activity was 3580.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 94.0% e.e.
  • a 200 ml reaction container was, after the air in the container was replaced by nitrogen, charged with 2.7 g (2.45 mmol) of [RuI(p-cymene) ⁇ (S)-SEGPHOS)]I and 110 ml of deaerated DMF, and the mixture was stirred at 75° C. for 16 hours. The mixture was cooled to 40° C. and DMF was withdrawn. Then, under the nitrogen atmosphere, 0.422 g (2.45 mmol) of NaOTf was introduced into the mixture, and 20 ml of methylene chloride and 20 ml of deaerated water were further added to the resulting mixture, followed by stirring for 16 hours.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.3 g (yield: 95.0%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.9 g (yield: 94.3%) of the titled compound.
  • a 200 ml reaction container was, after the air in the container was replaced by nitrogen, charged with 2.7 g (2.45 mmol) of [RuI(p-cymene) ⁇ (S)-SEGPHOS)]I, 0.421 g (2.45 mmol) of NaOTf and 110 ml of deaerated DMF, and the mixture was stirred at 75° C. for 16 hours. The mixture was cooled to 40° C., and DMF was withdrawn. Then, under the nitrogen atmosphere, 20 ml of methylene chloride and 20 ml of deaerated water were added to the resulting mixture, followed by stirring for 30 minutes.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.2 g (yield: 90.9%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 2.03 g (yield: 98.5%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 30 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 3.09 g (yield: 119.4%) of the titled compound.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 10 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 0.87 g (yield: 121.6%) of the titled compound.
  • a stainless autoclave with a volume of 500 ml was charged with 33.59 g (0.034 mmol) of [Ru--I 1 .5 - ⁇ (S)-SEGPHOS) ⁇ ] 2 (OTf), 20.55 g (244.6 mmol) of 4-methylene-2-oxetanone, 80 ml of tetrahydrofuran and 0.45 g of deaerated water under nitrogen, and the mixture was stirred at a reaction temperature of 50° C. under a hydrogen pressure of 50 kg/cm 2 for 15 hours.
  • the resulting reaction solution was distilled using a Claisen tube distiller, to obtain 19.1 g (yield: 90.8%) of a fraction having a boiling point of 71-73° C./29 mmHg (3866 Pa).
  • the conversion rate of this reaction was 90.8%, and the turn-over number measured to evaluate the catalytic activity was 6530.
  • a gas chromatography analysis effected by comparison to a standard material showed that the resultant product was 4-methyl-2-oxetanone.
  • the product was subjected to a gas chromatography (GC) analysis using an optically active column (Chiraldex G-TA 30 m, manufactured by ASTEC). The result of the analysis showed that the resultant product was an (R) isomer and the optical purity was 94.5% e.e.
  • Example 48 The same procedures as in Example 48 were carried out, except that 35.84 mg (0.0368 mmol) of [Ru--I 1 .5 - ⁇ (S)-SEGPHOS) ⁇ ] 2 (PF 6 ) and 20.38 g (242.62 mmol) of 4-methylene-2-oxetanone were used, to obtain 13.7 g (yield: 65.6%) of the titled compound.
  • the conversion rate of this reaction was 65.6%, and the turn-over number measured to evaluate the catalytic activity was 4320.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 95.5% e.e.
  • Example 48 The same procedures as in Example 48 were carried out, except that 36.75 mg (0.0364 mmol) of [Ru--I 1 .5 - ⁇ (S)-SEGPHOS) ⁇ ] 2 (OTs) and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 13.88 g (yield: 67.78%) of the titled compound.
  • the conversion rate of this reaction was 68.79%, and the turn-over number measured to evaluate the catalytic activity was 4500.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 95.6% e.e.
  • Example 48 The same procedures as in Example 48 were carried out, except that 33.98 mg (0.0364 mmol) of [Ru--I 1 .5 - ⁇ (S)-SEGPHOS) ⁇ ] 2 (OMs) and 20.42 mg (243.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 14.55 g (yield: 69.6%) of the titled compound. The conversion rate of this reaction was 69.6%, and the turn-over number measured to evaluate the catalytic activity was 4650. The measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 94.8% e.e.
  • Example 48 The same procedures as in Example 48 were carried out, except that 44.65 mg (0.0476 mmol) of [Ru--I 1 .5 - ⁇ (S)-SEGPHOS) ⁇ ] 2 (ClO 4 ) and 20.29 mg (241.55 mmol) of 4-methylene-2-oxetanone were used, to obtain 17.59 g (yield: 84.7%) of the titled compound.
  • the conversion rate of this reaction was 84.7%, and the turn-over number measured to evaluate the catalytic activity was 4300.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 95.4% e.e.
  • Example 48 The same procedures as in Example 48 were carried out, except that 25.0 mg (0.0238 mmol) of [Ru--I 1 .5 - ⁇ (S)-SEGPHOS) ⁇ ] 2 ⁇ OS(O) 2 C 4 F 9 ⁇ and 20.34 mg (242.1 mmol) of 4-methylene-2-oxetanone were used, and the stirring was continued for 15 hours at a reaction temperature of 60° C. under a hydrogen pressure of 40 kg/cm 2 , to obtain 18.99 g (yield: 91.2%) of the titled compound. The conversion rate of this reaction was 100%, and the turn-over number measured to evaluate the catalytic activity was 10180. The measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 94.4% e.e.
  • Example 48 The same procedures as in Example 48 were carried out, except that 22.85 mg (0.0198 mmol) of [Ru--I 1 .5 - ⁇ (S)-SEGPHOS) ⁇ ] 2 ⁇ OS(O) 2 C 8 F 17 ⁇ and 20.54 g (244.5 mmol) of 4-methylene-2-oxetanone were used, and the stirring was continued for 15 hours at a reaction temperature of 60 ⁇ and under a hydrogen pressure of 40 kg/cm2, to obtain 18.45 g (yield: 87.7%) of the titled compound. The conversion rate of this reaction was 87.7% and the turn-over number measured to evaluate the catalytic activity was 10830. The measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 93.8% e.e.
  • the ruthenium-iodo-optically active phosphine complex described in JP-A No. H7-206885 was produced. Using this phosphine complex as catalyst, optically active 4-methyl-2-oxetanone was produced.
  • Example 12 The same procedures as in Example 12 were carried out, except that 139.0 mg (0.119 mmol) of [RuI(p-cymene)((S)--T-BINAP)]I and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 9.50 g (yield: 47.5%) of the titled compound.
  • the conversion rate of this reaction was 48.0%, and the turn-over number measured to evaluate the catalytic activity was 960.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 92.8% e.e.
  • Example 12 The same procedures as in Example 12 were carried out, except that 215.5 mg (0.238 mmol) of [Ru(CH 3 COO) 2 [(S)--T-BINAP] and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used, to obtain 11.0 g (yield: 55.0%) of the titled compound.
  • the conversion rate of this reaction was 56.6%, and the turn-over number measured to evaluate the catalytic activity was 570.
  • the measurement of the absolute configuration showed that the resultant product was an (R) isomer and the optical purity was 93.6% e.e.
  • the catalytic activity (turn-over number), configuration and optical purity (%e.e.) of 4-methyl-2-oxetanone in Examples 12-19, 31-38, 46-50 and Comparative Examples 1-3 are shown collectively in Table 1.
  • a 100 ml eggplant-shape flask was, after the air in the flask was replaced by nitrogen, charged with 685 mg (0.700 mmol) of [RuI 2 (p-cymene)] 2 , 863 mg (1.414 mmol) of (S)-SEGPHOS, 239 mg (0.707 mmol) of KONf and 35 ml of deaerated acetonitrile, and the mixture was stirred at 80° C. for 16 hours. The mixture was cooled to 40° C. and acetonitrile was withdrawn under reduced pressure. Then, in the nitrogen atmosphere, 20 ml of methylene chloride and 20 ml of deaerated water were added to the resulting mixture, followed by stirring for 10 minutes.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 1.6 g (yield: 89.7%) of the titled compound.
  • a 20 ml eggplant-shape flask was, after the air in the flask was replaced by nitrogen, charged with 35 mg (0.122 mmol) of [RuI(p-cymene) ⁇ (S)-SEGPHOS ⁇ ]I, 20.9 mg (0.0619 mmol) of KONf and 3 ml of deaerated acetonitrile, and the mixture was stirred for 16 hours.
  • the mixture was cooled to 40° C., and acetonitrile was withdrawn under reduced pressure. Then, in the nitrogen atmosphere, 10 ml of methylene chloride and 10 ml of deaerated water were added to the resulting mixture, followed by stirring for 10 minutes.
  • the methylene chloride layer was extracted into a sampling syringe and washed with 20 ml of deaerated water, followed by distilling methylene chloride under reduced pressure. The resulting complex was then dried at 30° C. under reduced pressure for 4 hours, to obtain 130mg (yield: 84.1%) of the titled compound.
  • a 20 ml eggplant-shape flask was, after the air in the flask was replaced by nitrogen, charged with 60 mg (0.0613 mmol) of [RuI 2 (p-cymene)] 2 , 75.7 mg (0.124 mmol) of (S)-SEGPHOS, 11.7 mg (0.0619 mmol) of KOTf and 3 ml of deaerated acetonitrile, and the mixture was stirred at 80° C. for 16 hours. The mixture was cooled to 40° C., and acetonitrile was withdrawn under reduced pressure.

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Cited By (4)

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US6156692A (en) * 1996-04-30 2000-12-05 Bp Amoco Corporation Ruthenium-containing catalyst composition for olefin metathesis
US6171995B1 (en) * 1996-11-15 2001-01-09 Ciba Specialty Chemcials Corporation Catalyst mixture for ring-opening metathesis polymerization
US6214763B1 (en) * 1997-05-20 2001-04-10 Firmenich Sa Ruthenium catalysts and their use in the asymmetric hydrogenation of weakly coordinating substrates
US20040260101A1 (en) * 2001-09-28 2004-12-23 Sebastien Duprat De Paule Novel diphosphines, their complexes with transisition metals and their use in asymmetric synthesis

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JP4601779B2 (ja) * 2000-07-25 2010-12-22 高砂香料工業株式会社 光学活性アルコールの製造方法
CA2556891C (fr) 2004-02-19 2012-12-18 Lonza Ag Procede de preparation de 3-aminoalcools 1-substitues enantiomeriquement purs
EP1609795A1 (fr) * 2004-06-25 2005-12-28 Lonza AG Procédé de préparation de Biaryldiphosphines asymétriquement substituées
JP4519912B2 (ja) * 2004-06-25 2010-08-04 ロンザ アーゲー 非対称的に置換されたビアリールジホスフィンの調製方法
FR2952638A1 (fr) 2009-11-17 2011-05-20 Univ Strasbourg Procede de phosphination catalytique double ou triple de composes di, tri ou tetrahalobiaryles, intermediaires employes, composes obtenus et leurs utilisations

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US4691037A (en) * 1984-09-04 1987-09-01 Takasago Perfumery Co., Ltd. Ruthenium-phosphine complex
US5306834A (en) * 1992-07-16 1994-04-26 Takasago International Corporation Process for preparing optically active 4-methyl-2-oxetanone
US5412109A (en) * 1992-07-16 1995-05-02 Takasago International Corporation Process for preparing optically active 4-methyl-2-oxetanone

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JP3919268B2 (ja) * 1996-11-08 2007-05-23 高砂香料工業株式会社 ルテニウム−光学活性ホスフィン錯体、その製法およびこれを用いた光学活性４−メチル−２−オキセタノンの製造方法
JP3148136B2 (ja) * 1996-12-26 2001-03-19 高砂香料工業株式会社 新規なキラルジホスフィン化合物、その製造中間体、該ジホス フィン化合物を配位子とする遷移金属錯体並びに該錯体を含む 不斉水素化触媒

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US4691037A (en) * 1984-09-04 1987-09-01 Takasago Perfumery Co., Ltd. Ruthenium-phosphine complex
US5306834A (en) * 1992-07-16 1994-04-26 Takasago International Corporation Process for preparing optically active 4-methyl-2-oxetanone
US5412109A (en) * 1992-07-16 1995-05-02 Takasago International Corporation Process for preparing optically active 4-methyl-2-oxetanone

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6156692A (en) * 1996-04-30 2000-12-05 Bp Amoco Corporation Ruthenium-containing catalyst composition for olefin metathesis
US6171995B1 (en) * 1996-11-15 2001-01-09 Ciba Specialty Chemcials Corporation Catalyst mixture for ring-opening metathesis polymerization
US6214763B1 (en) * 1997-05-20 2001-04-10 Firmenich Sa Ruthenium catalysts and their use in the asymmetric hydrogenation of weakly coordinating substrates
US6455460B1 (en) 1997-05-20 2002-09-24 Firmenich Sa Ruthenium catalysts and method for making same
US20040260101A1 (en) * 2001-09-28 2004-12-23 Sebastien Duprat De Paule Novel diphosphines, their complexes with transisition metals and their use in asymmetric synthesis
US6878665B2 (en) * 2001-09-28 2005-04-12 Synkem Diphosphines, their complexes with transisition metals and their use in asymmetric synthesis

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